Process for metallized vias in polyimide

ABSTRACT

A process for producing a plurality of metallized vias in a polyimide dielectric is disclosed. The process includes depositing a polyimide precursor, then a silane and finally a metal, after patterning the polyimide and silane. The sandwich is heated to completely imidize the polyimide, crosslink the silane and anneal the metal simultaneously. The excess metal overlying the polyimide between the vias is removed by chemical mechanical polishing using the crosslinked silane as a polish stop.

FIELD OF THE INVENTION

The invention relates to a process for forming metallized vias in apolyimide layer on a substrate. The process is useful for thefabrication of semiconductor devices. The invention also relates tosemiconductor devices having metallized polyimide layers and asilsesquioxane layer overlying them.

BACKGROUND OF THE INVENTION

In the later steps of IC chip fabrication, it is common to wire thedevice by creating an appropriate pattern of metallic conductorsseparated by a low dielectric insulator on the surface of the chip. Thelower the dielectric constant of the insulator, the more densely thewiring can be packed without compromising electrical integrity. Becauseof its low dielectric constant and its convenience in fabricationprocesses, polyimide has become a material of choice.

A particularly attractive process for metallization of the preferredpolyimide dielectric would include the deposition of the polyimide layerand patterning with a series of trenches followed by the deposition of asuitable highly conductive metal in the trenches to form theconnections. In a particular and advantageous application of thisprocess, the metal would be copper or a copper alloy and would bedeposited by evaporation or sputtering. The excess metal overlying thepolyimide between the trenches would then be removed bychemical-mechanical polishing (CMP) back to the polyimide. (See FIGS. 1to 4.)

Unfortunately, the theoretically attractive process described above doesnot work in practice. There are two problems, both of which arise fromCMP: (1) the copper is pulled out of the trenches by the CMP and (2) thesurface of the polyimide is badly scored by the CMP. One way around theproblems is to replace polyimide by a different dielectric such assilicon oxide or nitride. Copper is then less prone to being pulled outof the trench because it adheres better, and the oxide or nitride isless prone to mechanical damage by CMP. One drawback is that thedielectric constants of oxide and nitride are significantly higher thanthat of polyimide. This drawback could possibly be overcome bydepositing a layer of polyimide and then coating the polyimide withoxide or nitride, but the deposition of oxide or nitride is done attemperatures that render polyimide an unattractive substrate because ofoutgassing and decomposition in the deposition tool. Moreover, there isvery high stress between a polyimide and an oxide or nitride layer, sothat the layers tend to crack and fail.

Thus there is a need for a process whereby a metallization can bedependably and reproducibly patterned in a polyimide layer.

There is a further need for a process that allows CMP of a metal thathas been deposited on a polyimide substrate.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a process whereby ametal can be dependably and reproducibly patterned in a polyimide layer.

It is a further object to allow CMP on a metal deposited on a polyimidesubstrate.

These and other objects, features and advantages are realized in thepresent invention, which in one aspect relates to a process forproducing a plurality of metallized vias in a polyimide layer on asubstrate comprising the steps of:

(a) applying a solution of a polyimide precursor in an inert solvent tothe substrate;

(b) heating, in a first heating cycle, the solution of polyimideprecursor at a combination of temperature and pressure sufficient tovolatilize the inert solvent but insufficient to completely convert thepolyimide precursor to polyimide. The first heating cycle is continuedfor a period of time at least sufficient to provide a mechanicallystable layer;

(c) applying a solution containing a polyaminoalkylalkoxysilane (PAAS)in an inert, nonaqueous solvent to the mechanically stable layer ofpolyimide precursor. A preferred genus of polyaminoalkylalkoxysilane hasthe formula ##STR1## wherein R¹ is hydrogen or alkoxy of one to fourcarbons, R² is a linear, branched or cyclic polyaminoalkyl residue ofone to eleven carbons, five to 26 hydrogens and two or three nitrogensand R³ is aryl or alkyl of one to four carbons;

(d) heating, in a second heating cycle, the solution of a PAAS at acombination of temperature and pressure sufficient to volatilize theinert solvent but insufficient to completely imidize the polyimideprecursor and insufficient to cleave a significant portion of the aminofunctions in the PAAS. The second heating cycle is continued for aperiod of time at least sufficient to provide a mechanically stablesilane layer;

(e) patterning both of the layers with a plurality of trenches;

(f) depositing sufficient metal to at least fill the trenches;

(g) heating, in a third heating cycle, the whole stack at a temperatureand for a time sufficient to completely imidize the polyimide and toconvert the silane layer to a silsesquioxane polymer layer; and

(h) chemical-mechanical polishing the substrate to remove all of themetal outside the trenches, using the layer of silsesquioxane as apolish stop.

First and second heating cycles are optimally carried out at from 100°to 200° C., and the third heating cycle is optimally at from 350° to450° C. In a preferred process, the polyimide precursor is a polyamicacid and the metal is copper or an alloy of copper. A preferred PAAS isN-[3-(trimethoxysilyl)propyl]-1,2-ethanediamine. The silsesquioxanelayer is preferably from 200 to 500 Å thick.

The solution containing a PAAS may also contain one or moreorganosilicon compounds selected from the group consisting ofarylalkoxysilanes and arylsilazanes. A preferred solution containing aPAAS consists essentially of a 1 to 5% solution ofN-[3-(trimethoxysilyl)propyl]-1,2-ethanediamine plusphenyltriethoxysilane. Throughout the text that follows, substituentsare defined when introduced and retain that definition whenever theyappear subsequently.

In another aspect the invention relates to a process for producing aplurality of metallized vias in a preformed polyimide layer on asubstrate comprising the steps of:

(a) applying a solution containing a PAAS in an inert, non-aqueoussolvent to the polyimide layer;

(b) heating, in a first heating cycle, the solution of a PAAS at acombination of temperature and pressure sufficient to volatilize theinert solvent but insufficient to cleave a significant portion of theamino functions in the PAAS. The first heating cycle is continued for aperiod of time at least sufficient to provide a mechanically stablesilane layer;

(c) patterning both layers with a plurality of trenches;

(d) depositing sufficient metal to at least fill the trenches;

(e) heating, in a second heating cycle, the metal, silane and polyimideat a temperature and for a time sufficient to convert the silane layerto a silsesquioxane polymer layer; and

(f) chemical-mechanical polishing the substrate to remove all of themetal outside the trenches using the layer of silsesquioxane as a polishstop.

Preferred materials and conditions are as before.

In another aspect the invention relates to a process for producing aplurality of metallized vias in a polyimide layer, having an upper andlower surface, comprising providing a 200 to 500 Å thick layer of asilsesquioxane on the upper surface of the polyimide layer and using thesilsesquioxane layer as a polish stop. The silsesquioxane layer isderived at least in part from a polyaminoalkylalkoxysilane (PAAS). Thepolish stop allows chemical mechanical polishing for removingmetallization deposited on the silsesquioxane layer while leavingmetallization deposited in a plurality of recessed structures in thepolyimide layer. Upper and lower, as used in the sense above, refer notto orientation with respect to gravity in an absolute sense butorientation with respect to gravity when the chip is in its normalorientation, i.e. substrate 8 on the bottom. Thus the "lower" surface isthe surface in contact with the substrate.

In another aspect the invention relates to semiconductor devices havingmetallized vias made by the foregoing processes, and particularly to alayered semiconductor device comprising:

(a) at least one layer of polyimide, which has a plurality of metallicinclusions; and

(b) a 200 to 500 Å thick layer of a silsesquioxane, derived at least inpart from a diaminoalkyltrialkoxysilane (PAAS), overlying the layer ofpolyimide.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1 to 4 are sequential schematic diagrams of a cross-section of adevice fabricated by the process of the invention;

FIG. 5 is a photomicrograph of a metallized via that has been fabricatedaccording the process of the invention; and

FIG. 6 is a photomicrograph of a metallized via illustrating a failuremode from fabrication not in accordance with the process of theinvention.

DETAILED DESCRIPTION OF THE INVENTION

As shown in FIGS. 1 to 4 the process of the invention allows one tocreate metallized vias in a polyimide layer 1 by overcoating with asilsesquioxane 2, patterning the polyimide and silsesquioxane to providetrenches 3, depositing metal 4, and CMP planarizing back to thesilsesquioxane layer 2. The process has a number of advantages,particularly in that the silsesquioxane can be applied by a simpleprocess, such as spin coating, which is compatible with polyimidedeposition processes. In addition, the resulting silsesquioxane layerhas mechanical properties very similar to those of polyimide so thatcracking and delamination are not problems.

According to the process of the invention, the polyimide may bepreformed or can be deposited and partially cured. Suitable polyimideprecursor materials include polyamic acid polymers which are based onthe condensation of aromatic dianhydrides with diamines, more preferablyaromatic diamines, and the corresponding polyamic ester polymers.Suitable aromatic dianhydrides include pyromellitic dianhydride,2,2-bis(3,4-dicarboxyphenyl)propane dianhydride,2,3,6,7-naphthalenetetracarboxylic dianhydride,2,2'3,3'-diphenyltetracarboxylic dianhydride, and benzophenonetetracarboxylic dianhydride. Suitable diamines include m-phenylenediamine, p-phenylene diamine and 4,4'-diaminophenyl ether. Illustrativepolyimide precursor materials useful for the purposes of this inventionand their methods of preparation are disclosed in U.S. Pat. Nos.3,179,614, 3,264,250 and 4,612,210, the disclosures of which areincorporated herein by reference. Particularly preferred polyamic acidpolymers are available from E. I. duPont deNemours and Company,Wilmington, Del., under the trade designation "PI-5810", "PI-2545" and"PI-2525".

Typically, the polyimide precursor is dissolved in a suitable inertsolvent, and then the solution is applied to the substrate by spincoating, at a spin speed of about 1000-7000 rpm, depending upon thedesired thickness. The solvents are not unduly limited, and a number ofsolvents or solvent mixtures can be used, for example,N-methylpyrrolidinone (NMP), dimethylacetamide (DMAc), dimethylformamide(DMF), dimethylsulfoxide (DMSO) or suitable mixtures of these solventswith various conventional hydrocarbon solvents.

After applying the solution, the surface is heated to drive off solventfrom the polyimide precursor material. The actual heating conditions,i.e. temperature, pressure and time, may vary over wide ranges and aregenerally dependent on the monomers employed in the organic solution andtheir molar ratios, the polyimide precursor material employed, thedesired thickness of the cured layers being produced, as well as otherfactors which are apparent to those skilled in the art. Typicalthickness would be from 0.5 to 2.0 μm. In general, temperatures below200° C., for a period of about 15-60 minutes at atmospheric pressureprovide a mechanically stable polyimide layer. By "mechanically stable"is meant that the layer does not creep and does not alter dimension orrelease gases on further processing. Outgassing is a particular concernbecause it causes delamination of metal layers.

In a preferred embodiment, the heat treatment is performed in a seriesof steps at atmospheric pressure. In this manner, the substrate isexposed to a temperature of about 85°-160° C., or sequentialtemperatures within that range, to drive off solvent.

In some instances it may be desirable to completely cure the polyimidelayer before depositing the silsesquioxane precursor solution. This canbe accomplished by heating to 350° to 450° C. to form the polyimidepolymer from the polyamic acid. The process of cyclization of polyamicacid or ester precursors to polyimide is referred to as "imidizing".Completely imidizing before converting the silane to silsesquioxanepolymer is generally less advantageous than the simultaneous, finalcuring of polyimide and silsesquioxane described below, and in apreferred process less than 80% of the polyamic acid is imidized duringvolatilization of the solvent.

After the polyimide precursor layer has been deposited and made stable,the silane layer is deposited, preferably by spin-coating at 500 to10000 rpm, depending on the thickness of the desired layer. For thepurposes of the invention, layers 200 to 500 Å in thickness are optimal.Copolymers can be made by including, in addition to the PAAS, anarylalkoxysilane or arylsilazane. The silane can be coated as a 1 to 5%solution in an inert, organic solvent. Aminoalkylsilanes are known foruse as adhesion agents between polyimide and oxide substrates, but inthe art they are not used as discrete layers of measurable thickness.Such aminoalkylsilanes are used as 0.1% solutions to produce monolayers.

Any suitable solvent which can dissolve the PAAS and thearylalkoxysilane or arylsilazane can be employed. Typical solventsinclude, for example, alcohols, such as methanol, ethanol, propanol,isopropanol, butanol, isobutanol, isoamyl alcohol, and the like; ethers,such as the cellosolves, e.g. methyl cellosolve, diglyme, dioxane, butylcarbitol, tetrahydrofuran, and the like; aromatic alcohols, such asphenol, and the like; polyhydric alcohols, such as ethylene glycol,tetramethylene glycol, and the like; ketones, such as methyl ethylketone, methyl isobutyl ketone, diethyl ketone, and the like; etc., aswell as mixtures thereof, as will be apparent to those skilled in theart. Preferred solvents include methanol, ethanol and isopropanol.

The PAAS is of the genus ##STR2## wherein R¹ is hydrogen or alkoxy ofone to four carbons, R² is a linear, branched or cyclic polyaminoalkylresidue of empirical formula C₁₋₁₁ H₅₋₂₆ N₂₋₃ and R³ is as before. Apreferred PAAS is N-[3-(trimethoxysilyl)propyl]-1,2-ethanediamine(Registry Number 1760-24-3), also known asN-β-aminoethyl-γ-aminopropyltrimethoxy-silane, which is sold by UnionCarbide (Danbury, Conn.) under the designation of Z6020 and by HulsAmerica (Piscataway, N.J.) under the designation of A0700. Otherrepresentative PAAS's includeN-β-aminoethyl-γ-aminopropyltris-(β-ethylhexoxy)silane;trimethoxysilylpropyldiethylenetriamine;(aminoethylaminomethyl)phenethyltrimethoxysilane;(aminoethylaminomethyl)phenyltrimethoxysilane;N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane; and1,4-bis[3-(trimethoxysilyl)propyl]-ethylenediamine. The importantfeature for the purpose of the invention appears to be the presence ofat least two amino functionalities. Thus when the same process as thatof the invention was carried out using the commercially availableadhesive 3-aminopropyltriethoxysilane (ATS) in place ofN-[3-(trimethoxysilyl)propyl]-1,2-ethanediamine (a PAAS) there wassignificant delamination of the metal structures. A working hypothesisis that a minimum of two amino functionalities is required to bind themetal, particularly copper, more tightly and thereby provide betteradhesion.

Amine-containing side chains appear to be pyrolytically removed at hightemperatures. As these are lost, the sites for binding to the metalsignificantly decrease; this is the reason for controlling the time andtemperature of the baking operations, particularly those that precedemetal deposition, so as to preserve as many binding sites as possible.At least half of the amino functions should always remain in the silaneafter baking and before metal deposition.

Heating the PAAS causes a reaction to produce what appears to be aladder-type silsesquioxane polymer, although the invention is not to berestricted to this interpretation. So-called "ladder-type"silsesquioxane polymers and copolymers analogous to those of theinvention, but made from monoamines in the presence of water, aredescribed in U.S. Pat. No. 4,981,530, the disclosure of which isincorporated herein by reference. The silsesquioxane polymers andprecursors of the present invention differ from those of U.S. Pat. No.4,981,530 in having alkoxyl functionalities in place of hydroxyl anddiamine and triamine in place of monoamine side chains.

Preferred optional arylalkoxysilane or arylsilazane monomers that may beadded to prepare silsesquioxane copolymers are represented by theformula:

    R.sup.4 Si(OR.sup.3).sub.3

wherein R⁴ is an unsubstituted or substituted phenyl or benzyl residue.Also, mixtures of such arylalkoxysilanes and arylsilazanes can be used.Representative arylalkoxysilane and arylsilazane monomers include thefollowing: phenyltriethoxysilane, tris(dimethylamino) phenysilane,bis(dimethylamino)diphenylsilane, 4-pyridyltrimethoxysilane andbis(dimethylamino) methyl phenyl silane. Particularly preferredarylalkoxysilane and arylsilazane monomers include those in which R⁴ isan unsubstituted or substituted phenyl group. Arylalkoxysilane monomers,such as phenyltrialkoxysilane, are most preferred, e.g.phenyltriethoxysilane.

The coated surface is then heated at a temperature which is sufficientto drive off the solvent and form a partially cured layer. It is notnecessary to fully cure the layer at this point; in fact, it is onlydesired to cure the layer to the extent that it has sufficient integrityfor patterning and metallization in the next steps. Generally speaking,the temperature will usually range from about 85° to about 200° C.,preferably from about 90° to about 180° C., for a time ranging fromabout 0.5 to about 20 minutes, preferably from about 5 to about 10minutes. However the actual conditions of partial curing may varybroadly depending upon a number of factors, such as the particularmonomers employed in the organic solution, as well as their molarratios, etc., as should be apparent to those skilled in the art.Generally, it is desirable to remove at least about 90% of the solventto produce a mechanically stable layer. Baking is preferably done underan inert atmosphere (nitrogen) and must be done in an inert atmosphereif the temperature is above 150° C.

Next, as shown in FIG. 1, a photoresist 6 is deposited, planarized,exposed and developed by procedures well-known in the art. Using thephotoresist as a mask, trenches 3 are etched through the polyimide 1 andthe silane 2 to the substrate 8, which will commonly include aconductive layer for electrical contact in portions of the vias beingproduced.

As shown in FIG. 3, a layer of metal 4 is deposited by evaporation,sputtering or other technique compatible with the substrate and stack.For most applications a highly conductive metal such as copper or itsalloys will be preferred. However other metals may also be used. Typicalmetals include transition metals or alloys of transition metals,refractory metals or silicides of refractory metals, etc., for example,copper, aluminum, silver, chromium, lead, tin, gold, the Groups IVA, VAand VIA metals, such as titanium and tungsten, and so forth. Aluminum,nickel and titanium are preferred over such refractory metals astungsten because they can be deposited at lower temperature.

After deposition the whole stack is heated at sufficient temperature,pressure and duration to cure (or imidize) the polyimide, to formsilsesquioxane from the silane layer and to anneal the metal.

Apparently, during the curing step, the copolymer coordinates to themetal through the amino groups. In addition, the copolymer seems tofurther react with the polyimide precursor to form an amine salt whichimidizes in the usual fashion, forming a covalent attachment through theamino groups. In any event, the layer of cured silsesquioxane copolymerprovides a strong bond between the polyimide layer and the metalsurface. The silsesquioxane from a PAAS has been found to demonstrateexcellent mechanical characteristics and desirable electricalproperties, such as low dielectric constant, which can be made evenlower by increasing the proportion of arylsilane. As a furtherprocessing advantage, the adhesion promoting layer is formed withoutrequiring a separate, full curing step.

In a final step, as shown in FIG. 4, the excess metal 4 is removed fromthe surface of the dielectric by CMP. Chemical-mechanical polishing iswell-known in the art and is described for example in U.S. Pat. Nos.4,954,142 and 4,944,836, the disclosures of which are incorporatedherein by reference. CMP compositions commonly comprise an abrasive,such as silica or alumina, a surfactant, an antioxidant (to protect thesurface of the metal) and a buffer to adjust the pH of the compositionfor optimum selectivity and efficacy. In the process of the invention,the adhesion between the silsesquioxane 2 on top of the polyimide andmetal 4 (see FIG. 3) allows CMP without delamination. When the CMPreaches the surface of silsesquioxane, the silsesquioxane provides apolish stop which protects the surface of the polyimide layer 1 frommechanical damage by the abrasive in the CMP composition. By the timethe metal layer is abraded and etched to the level of the top of thetrenches, the abrasive can no longer get enough purchase to pull metalout of the trenches and the metallization remains undisturbed despitethe absence of a silsesquioxane layer within the trench.

The physical properties of silsesquioxane are particularly advantageousfor use in CMP on polyimide because they are well matched to those ofpolyimide in aqueous environments. (The CMP slurry is water-based.) Atraditional oxide would delaminate from the polyimide or would crackbecause the polyimide absorbs up to 4% water from the CMP slurry duringCMP, while oxide does not; the silsesquioxanes of the invention absorbat least as much water as the polyimide and so do not crack ordelaminate.

EXAMPLE 1

A conventional monoamine solution (0.1% 3-aminopropyltriethoxysilane inwater) was applied to silicon substrate wafers and let stand for 15sec., then spun at a speed of 3,000 rpm for 30 seconds. The substrateswere then heated at a temperature of 100° C. for 10 minutes to removeexcess methanol.

Following that, a solution of polyamic acid (11% solids, based onbiphenylene tetracarboxylic dianydride and p-phenylene diamine,commercially available from E. I. duPont deNemours and Company under thedesignation "PI-5810") in NMP was spin applied at an initial spin speedof 500 rpm for 15 seconds, followed by a final spin speed of 3000 rpmfor 30 seconds. The wafers were then baked in air on an 8-positionhotplate at temperatures of 95°/105°/105°/115°/115° C. for 2.5 minuteseach and then 20 minutes at 135° at ambient pressure. A solution of 2%N-[3-(trimethoxysilyl)propyl]-1,2-ethanediamine in methanol was applied,let stand 15 seconds and spun at 2000 to 4000 rpm for 30 seconds. Thewafers were baked at 100° C. for 10 minutes and 185° to 200° for 20minutes in an inert atmosphere. A photoresist was applied, exposed,developed and baked by a standard process and a series of trenchesetched by RIE with 80:20 CF₄ /O₂ then 100% O₂. Copper was deposited byevaporation using a resistively heated source and unheated substrate.The deposition rate was 50 Å/sec at a background pressure of 1×10⁻⁷torr. The whole stack was annealed at 400° C. for 45 minutes in anatmosphere of 10:90 H₂ /N₂. Excess copper was removed by CMP using anaqueous slurry of alumina, antioxidant and surfactant at pH 4.0.

The cured structures were examined visually and tested for resistanceand line continuity. Photomicrographs are shown in FIGS. 5 and 6. FIG. 5is an oblique view of an edge of a polyimide surface 1 coated withsilsesquioxane layer 2 after CMP as described in example 1; copper 4remains intact in the trenches. FIG. 6 is an oblique view of a polyimidesurface 1 lacking a silsesquioxane layer, as a result of which almostall of the copper 4 has been stripped from the trenches 3 by the sameCMP as in FIG. 5.

While the invention has been particularly shown and described withreference to preferred embodiments thereof, it will be understood bythose skilled in the art that other changes in form and details may bemade therein without departing from the spirit and scope of theinvention.

We claim:
 1. A process for producing a plurality of metallized vias in apolyimide layer on a substrate comprising the steps of:(a) applying asolution of a polyimide precursor in an inert solvent to said substrate;(b) heating, in a first heating cycle, said solution of polyimideprecursor at a combination of temperature and pressure sufficient tovolatilize said inert solvent but insufficient to completely convertsaid polyimide precursor to polyimide; and continuing said first heatingcycle for a period of time at least sufficient to provide a mechanicallystable layer; (c) applying a solution containing apolyaminoalkylalkoxysilane (PAAS) in an inert, nonaqueous solvent tosaid mechanically stable layer of polyimide precursor; (d) heating, in asecond heating cycle, said solution of a PAAS at a combination oftemperature and pressure sufficient to volatilize said inert solvent butinsufficient to completely imidize said polyimide precursor andinsufficient to cleave a significant portion of amino functions in saidPAAS, and continuing said second heating cycle for a period of time atleast sufficient to provide a mechanically stable silane layer; (e)patterning both of said layers of polyimide precursor and silane with aplurality of trenches; (f) depositing sufficient metal on said substrateto at least fill said trenches; (g) heating, in a third heating cycle,said metal, said silane layer and said polyimide precursor layer at atemperature and for a time sufficient to completely imidize saidpolyimide and to convert said silane layer to a silsesquioxane polymerlayer; and (h) chemical-mechanical polishing said substrate to removeall of said metal outside said trenches using said layer ofsilsesquioxane as a polish stop.
 2. The process of claim 1 wherein saidpolyaminoalkylalkoxysilane has the formula: ##STR3## wherein R¹ ishydrogen or alkoxy of one to four carbons, R² is a linear, branched orcyclic polyaminoalkyl residue of one to eleven carbons, five to 26hydrogens and two or three nitrogens and R³ is alkyl of one to fourcarbons or aryl.
 3. The process of claim 1 wherein said first and secondheating cycles are at from 100° to 200° C. and said third heating cycleis at from 350° to 450° C.
 4. The process of claim 1 wherein saidpolyimide precursor is a polyamic acid.
 5. The process of claim 1wherein said metal is copper or an alloy of copper.
 6. The process ofclaim 1 wherein said PAAS isN-[3-(trimethoxysilyl)propyl]1,2-ethanediamine.
 7. The process of claim1 wherein said silsesquioxane polymer layer is from 200 to 500 Å thick.8. The process of claim 1 wherein said solution containing a PAAS alsocontains one or more organosilicon compounds selected from the groupconsisting of arylalkoxysilanes and arylsilazanes.
 9. The process ofclaim 8 wherein said solution containing a PAAS consists essentially ofa 1 to 5% solution of N-[3-(trimethoxysilyl)propyl]-1,2-ethanediamineplus phenyltriethoxysilane.
 10. A process for producing a plurality ofmetallized vias in a preformed polyimide layer on a substrate comprisingthe steps of:(a) applying a solution containing apolyaminoalkylalkoxysilane (PAAS) in an inert, non-aqueous solvent tosaid polyimide layer; (b) heating, in a first heating cycle, saidsolution of a PAAS at a combination of temperature and pressuresufficient to volatilize said inert solvent but insufficient to cleave asignificant portion of amino functions in said PAAS, and continuing saidfirst heating cycle for a period of time at least sufficient to providea mechanically stable silane layer; (c) patterning both of saidpolyimide and said mechanically stable silane layer with a plurality oftrenches; (d) depositing sufficient metal to at least fill saidtrenches; (e) heating, in a second heating cycle, said metal, silane andpolyimide at a temperature and for a time sufficient to convert saidsilane layer to a silsesquioxane polymer layer; and (f)chemical-mechanical polishing said substrate to remove all of said metaloutside said trenches using said layer of silsesquioxane as a polishstop.
 11. The process of claim 10 wherein said PAAS has the formula##STR4## wherein R¹ is hydrogen or alkoxy of one to four carbons, R² isa linear, branched or cyclic polyaminoalkyl residue of one to elevencarbons, five to 26 hydrogens and two or three nitrogens and R³ is alkylof one to four carbons or aryl.
 12. The process according of claim 10wherein said first heating cycle is at from 100° to 200° C. and saidsecond heating cycle is at from 350° to 450° C.
 13. The process of claim10 wherein said metal is copper or an alloy of copper.
 14. The processof claim 10 wherein said PAAS isN-[3-(trimethoxysilyl)propyl]-1,2-ethanediamine.
 15. The process ofclaim 10 wherein said silsesquioxane polymer layer is from 200 to 500 Åthick.
 16. The process of claim 10 wherein said solution containing aPAAS also contains one or more organosilicon compounds selected from thegroup consisting of arylalkoxysilanes and arylsilazanes.
 17. The processof claim 16 wherein said solution containing a PAAS consists essentiallyof a 1 to 5% solution of N-[3-(trimethoxysilyl)propyl]-1,2-ethanediamineplus phenyltriethoxysilane.
 18. A process for producing a plurality ofmetallized vias in a polyimide layer, having an upper and lower surface,comprising providing a 200 to 500 Å thick layer of a silsesquioxane,derived at least in part from a polyaminoalkylalkoxysilane (PAAS), onsaid upper surface of said polyimide layer and using said silsesquioxanelayer as a polish stop for removing, by chemical mechanical polishing,metallization deposited on said silsesquioxane layer while leavingmetallization deposited in a plurality of recessed structures in saidpolyimide layer.
 19. The process of claim 18 wherein said metallizationis copper or an alloy of copper.
 20. The process of claim 18 whereinsaid silsesquioxane is derived at least in part fromN-[3-(trimethoxysilyl)propyl]-1,2-ethanediamine.
 21. The process ofclaim 20 wherein said silsesquioxane layer is derived from a 1 to 5%solution of N-[3-(trimethoxysilyl)propyl]-1,2-ethanediamine andphenyltriethoxysilane.